JP2005247901A - 4-silyl-1-butene-3-yne polymer, copolymer with conjugated diene, and methods for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a novel polymer and a novel copolymer each comprising 4-silyl-1-butene-3-yne structural units. <P>SOLUTION: The 4-silyl-1-butene-3-yne polymer comprises structural units represented by formula (I) and structural units represented by formula (II). The copolymer comprises 4-silyl-1-butene-3-yne structural units and conjugated diene structural units. The method for producing the polymer or the copolymer comprises using a polymerization catalyst containing a rare earth metallocene complex. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel polymer, 4-silyl-1-butene-3-in polymer, a copolymer of 4-silyl-1-butene-3-yne and a conjugated diene, and a method for producing them. .

The 4-silyl-1-butene-3-yne polymer can theoretically have structural units represented by the following partial structural formulas (I) to (IV) (formula ( R ¹ in I) to (IV) represents, for example, an alkyl group having 1 to 5 carbon atoms). That is, as the structural unit, the structural unit (I) that is a 1,4-adduct, the structural unit (II) that is a 1,2-adduct, the structural unit (III) that is a 3,4-adduct, and 1,3 -Constituent units (IV) that are adducts are considered.

  So far, several reports have been made on a polymer of 4-trimethylsilyl-1-butene-3-yne (hereinafter also referred to as “TMSVA”), which is one of 4-silyl-1-butene-3-yne. (For example, refer to Patent Document 1 and Non-Patent Documents 1 to 5). However, in any report, the obtained polymer selectively has a structural unit represented by the structural formula (II), and a polymer containing a structural unit other than (II) has not been obtained.

  Furthermore, the conventional 4-silyl-1-butene-3-yne polymer is produced by polymerizing a 4-silyl-1-butene-3-yne compound, and the polymerization is performed by radical polymerization or anionic polymerization. It is done by. However, there is no report that the 4-silyl-1-butene-3-yne compound was polymerized using a coordination ion polymerization catalyst.

On the other hand, polymers of conjugated dienes have properties as rubber. For example, butadiene polymers and isoprene polymers are polymers widely used as rubber. Furthermore, the copolymer of conjugated diene and other monomers exhibits rubbery properties or plastic properties depending on the content of conjugated diene units, as well as conjugated diene polymers. However, it is known that various properties can be added depending on the type and amount of the other monomer. As the copolymer, styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR) and the like are widely known. Therefore, the copolymer of conjugated diene and 4-silyl-1-butene-3-yne is expected to be a polymer having new properties, but as described above, 4-silyl-1-butene-3 -There are no reports on the production of such copolymers under the circumstances where only limited polymerization methods are known for in-compounds.
Japanese Patent Publication No. 48-8874 Macromol. Chem. Phys. 2001, 202, No. 16, pp. 3099-3105. Eur. Polym. J. 1997, Vol.33, No 5. pp. 719-723. Macromolecules 1999, 32, pp. 238-240. Polymer Letters 1971, Vol. 9, pp. 275- 279 Journal of Polymer Science: Part A: Polymer Chemistry, 2001, Vol. 39, 1016-1023

  The inventors of the present invention are keen to produce a polymer of 4-silyl-1-buten-3-yne, which contains a structural unit other than the structural unit represented by the general formula (II). investigated. In particular, since the structural unit represented by the general formula (I) has an allene structure and π electrons spread, the polymer containing the structural unit (I) is expected to have unique properties. The Therefore, an object of the present invention is to provide a polymer of 4-silyl-1-butene-3-yne containing the structural unit represented by the general formula (I).

  Further, as described above, a copolymer of a conjugated diene and another monomer is a polymer having different properties from the homopolymer of the conjugated diene, and may be used as a plastic or rubber having new properties. is there. Therefore, an object of the present invention is to provide a copolymer of a conjugated diene and 4-silyl-1-butene-3-yne.

That is, the present invention is as follows.
(1) A 4-silyl-1-butene-3-yne polymer containing a structural unit represented by the following general formula (I) and a structural unit represented by the general formula (II).

(2) The molar ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) contained in the polymer is (I) :( II) = 10: 90 to The polymer according to (1), which is in a range of 100: 0.
(3) The polymer as described in (1) or (2), wherein R ¹ in the general formula (I) or the formula (II) is all a methyl group.
(4) A copolymer comprising 4-silyl-1-butene-3-yne polymer units (A) and conjugated diene polymer units (B).
(5) The 4-silyl-1-butene-3-yne polymer unit (A) includes a structural unit represented by the following general formula (I) and a structural unit represented by the general formula (II). The copolymer as described in (4) characterized by these.

(6) The molar ratio of 4-silyl-1-butene-3-yne polymer unit (A) to conjugated diene polymer unit (B) in the copolymer is (A) :( B) = 95: 5-2. The copolymer according to (4) or (5), wherein the copolymer is in the range of 98.
(7) The molar ratio of cis 1,4-constituent units to all constituent units contained in the conjugated diene polymerized unit (B) is in the range of 20 to 100 mol%, (4) to (4) The copolymer according to any one of 6).
(8) The copolymer according to any one of (4) to (7), wherein the conjugated diene is 1,3-butadiene.
(9) The co-polymer according to any one of (4) to (8), wherein the 4-silyl-1-butene-3-yne is 4-trimethylsilyl-1-butene-3-yne Coalescence.
(10) A polymer according to any one of (1) to (3), comprising a step of polymerizing a 4-silyl-1-butene-3-yne compound using a catalyst containing a rare earth metal metallocene complex. how to.
(11) The method according to any one of (4) to (9), including a step of polymerizing a 4-silyl-1-butene-3-yne compound and a conjugated diene compound using a catalyst including a rare earth metal metallocene complex. A method for producing a copolymer.
(12) The method according to (10) or (11), wherein the rare earth metal metallocene complex is a complex represented by the following general formula (α).

(13) The method according to any one of (10) to (12), wherein the catalyst further contains an ionic compound comprising a non-coordinating anion and a cation.

The polymer of 4-silyl-1-butene-3-yne of the present invention is a novel polymer, and has a unique partial structure (structural unit) having an allene structure as its structural unit. Expected to have. For example, application to optical recording disks, contact lenses, and the like is expected.
The copolymer containing 4-silyl-1-butene-3-yne unit and conjugated diene unit of the present invention is also a novel polymer, which is different from the conventional (co) polymer containing conjugated diene unit. It is expected to have properties and may be used as rubber or plastic. For example, the rubber is expected to be applied to the tread portion and carcass portion of a pneumatic tire, and the plastic is expected to be applied to an impact-resistant plastic material.

<4-silyl-1-butene-3-yne polymer of the present invention>
The 4-silyl-1-butene-3-yne polymer of the present invention (hereinafter also simply referred to as “the polymer of the present invention”) is an arbitrary constituent unit represented by the general formulas (I) to (IV). Preferably, at least the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) are included. More preferably, the polymer comprises a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II).

R ¹ in the structural units represented by the general formulas (I) to (IV) may be any group, but preferably represents a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. R ¹ is more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. Most preferably, all R ¹ are methyl groups, ie the most preferred polymer of the invention is a 4-trimethylsilyl-1-butene-3-yne polymer. The polymer of the present invention may be a copolymer of plural kinds of 4-silyl-1-butene-3-ynes having different R ¹ .

  The polymer of the present invention may contain the constituent units (I) and (II) in any ratio, but preferably the molar ratio of (I) to (II) is (I) :( II) = 10: 90. Within the range of ˜100: 0, preferably within the range of 15:85 to 50:50, and most preferably within the range of 17:83 to 22:78. The ratio can be calculated from the ratio of the integral value of the specific peak obtained by measuring the NMR spectrum of the resulting polymer. The calculation of this ratio is described in detail later in this specification.

  The weight average molecular weight of the polymer of the present invention may be any molecular weight, but is usually 5000 or more, preferably 10,000 or more, more preferably 20000 or more, and further preferably 120,000 or more. In addition, although the upper limit of a weight average molecular weight is not specifically limited, As a standard, it is 1000000. In the present invention, the weight average molecular weight can be measured using polystyrene as a standard substance by the GPC method. The measurement can be performed using, for example, a GPC measurement apparatus (TOSOH HLC-8220 GPC).

  The molecular weight distribution of the polymer of the present invention is usually 5.0 or less, preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.2 or less. In the present invention, the molecular weight distribution can be measured using polystyrene as a standard substance by the GPC method. The measurement can be performed using, for example, a GPC measurement apparatus (TOSOH HLC-8220 GPC).

  The polymer of the present invention has a silyl group, but all or part of the silyl group can be substituted with another atom or group such as a hydrogen atom. Methods for substituting a silyl group are well known, and those skilled in the art can appropriately select and perform the substitution. For example, hydrogen atoms can be replaced by alkali treatment or fluorine ion treatment, or various groups can be substituted by transmetalation using a transition metal catalyst or the like and reaction with halides. It is thought that you can.

<Copolymer of 4-silyl-1-buten-3-yne and conjugated diene of the present invention>
The copolymer of the present invention is a copolymer comprising 4-silyl-1-butene-3-yne polymerized units (A) and conjugated diene polymerized units (B). Also referred to as “inventive copolymer”). Preferably, it is a copolymer comprising 4-silyl-1-butene-3-yne polymerized units (A) and conjugated diene polymerized units (B).
The copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, a kraft copolymer, etc., preferably a random copolymer or a block copolymer, more preferably It is a random copolymer.

  The copolymer of the present invention contains 4-silyl-1-butene-3-yne polymer unit (A) and conjugated diene polymer unit (B) in an arbitrary ratio. Preferably, the molar ratio of 4-silyl-1-butene-3-yne polymer unit (A) and conjugated diene polymer unit (B) is within the range of (A) :( B) = 95: 5 to 2:98. is there. From the problem of providing a copolymer used for rubber, the molar ratio of (B) is preferably about 80 mol% or more, and from the problem of providing a copolymer used for plastic. It is preferable that the molar ratio of (B) is less than 80 mol%. The ratio can be calculated from the ratio of the integral value of a specific peak by measuring the NMR spectrum of the obtained polymer. The calculation of this ratio is described in detail later in this specification.

  The 4-silyl-1-butene-3-yne polymer unit (A) contained in the copolymer of the present invention may contain constituent units represented by the following general formulas (I) to (IV) in any ratio. . Preferably, it contains at least the structural units represented by (I) and (II), and more preferably comprises the structural units represented by (I) and (II). The molar ratio of the structural units (I) and (II) contained in the 4-silyl-1-butene-3-yne polymer unit (A) is in the range of (I) :( II) = 15: 85 to 50:50. It is preferably within the range, more preferably within the range of 20:80 to 40:60, and even more preferably within the range of 30:70 to 35:65. The ratio can be calculated from the ratio of the integral value of the specific peak obtained by measuring the NMR spectrum of the resulting polymer. The calculation of this ratio is described in detail later in this specification.

  The silyl group in the 4-silyl-1-butene-3-yne polymer unit (A) contained in the copolymer of the present invention has any three substituents. The substituents are, for example, each independently an alkyl group having 1 to 5 carbon atoms, preferably all methyl groups.

  The conjugated diene polymer unit (B) contained in the copolymer of the present invention includes the following structural units, that is, cis 1,4-structural unit (V), trans 1,4-structural unit (VI), or 1 , 2-constituent unit (VII), or, optionally, 3,4-constituent units, and these constituent units may be included in any ratio.

A to f in the general formulas (V) to (VII) are each an arbitrary atom or group, but preferably a to f are each independently a hydrogen atom or a lower alkyl group (for example, a methyl group or an ethyl group). It is. Most preferably, all of a to f are hydrogen atoms. (Ie 1,3-
It is a butadiene polymer unit. )

  All structural units contained in the conjugated diene polymerized unit (B) contained in the copolymer of the present invention (that is, cis 1,4-structural unit (V), trans 1,4-structural unit (VI), and 1, The molar ratio of the cis 1,4-constituent unit to the 2-constituent unit (VII) and, depending on the substituent, the sum of 3,4-constituent units) is preferably in the range of 20-100 mol%, more preferably 45-98 mol. It is in the range of%. The ratio can be calculated from the ratio of the integral value of a specific peak by measuring the NMR spectrum of the obtained polymer. The calculation of this ratio is described in detail later in this specification.

  The weight average molecular weight of the copolymer of the present invention may be arbitrary, but is at least 5,000 or more, usually 10,000 or more, preferably 50,000 or more, more preferably 140,000 or more. In addition, although the upper limit of a weight average molecular weight is not specifically limited, As a standard, it is 1000000. The weight average molecular weight in the present invention can be measured using polystyrene as a standard substance by the GPC method. The measurement can be performed using, for example, a GPC measurement apparatus (TOSOH HLC-8220 GPC).

  The molecular weight distribution of the copolymer of the present invention shows an arbitrary distribution, but is usually 5.0 or less, preferably 4.0 or less, more preferably 3.6 or less, and still more preferably 3.4 or less. The molecular weight distribution in the present invention can be measured using polystyrene as a standard substance by the GPC method using the obtained copolymer. The measurement can be performed using, for example, a GPC measurement apparatus (TOSOH HLC-8220 GPC).

<Method of producing 4-silyl-1-butene-3-yne polymer of the present invention and a copolymer with conjugated diene>
The 4-silyl-1-butene-3-yne polymer of the present invention can be produced by polymerizing a 4-silyl-1-butene-3-yne compound, and 4-silyl-1-butene- A copolymer containing 3-in polymerized units (A) and conjugated diene polymerized units (B) can be produced by copolymerizing a 4-silyl-1-butene-3-yne compound and a conjugated diene compound. The polymerization or copolymerization can be performed by any method such as an addition polymerization method, a polycondensation method, or a polyaddition method, but it can be preferably performed by an addition polymerization method using a polymerization catalyst.

Copolymerization of the 4-silyl-1-butene-3-yne compound and the conjugated diene compound can be performed by polymerizing a mixture of both monomers, and the copolymer thus obtained is a random copolymer, Or it may be an alternating copolymer. The copolymerization is carried out by first polymerizing the conjugated diene compound alone to form a so-called living polymer and then further polymerizing the 4-silyl-1-butene-3-yne compound (copolymerization by living polymerization). The copolymer obtained in this way can be a block copolymer. In the copolymerization by living polymerization, the order of polymerization of the conjugated diene compound and the 4-silyl-1-butene-3-yne compound can be arbitrary, but the conjugated diene compound is preferably polymerized first.

  Any amount of 4-silyl-1-buten-3-yne compound or conjugated diene compound can be polymerized. Needless to say, the higher the number of moles of the compound to be polymerized, the higher the weight average molecular weight.

  In the copolymerization of the 4-silyl-1-buten-3-yne compound and the conjugated diene compound, both monomers can be polymerized at an arbitrary ratio. By changing the ratio, the ratio of the 4-silyl-1-butene-3-yne polymer unit (A) and the conjugated diene polymer unit (B) in the copolymer can be adjusted. For example, when the molar ratio of the conjugated diene compound to the total of both monomer compounds to be polymerized is about 97 mol%, a copolymer containing about 98 mol% of the conjugated diene polymer unit (B) can be produced. On the other hand, when the molar ratio of the conjugated diene compound to the total of both monomer compounds is about 18 mol%, a copolymer containing about 9 mol% of the conjugated diene polymer unit (B) can be produced. Further, by adjusting the ratio of the conjugated diene polymer unit (B) in the copolymer in this way, the properties of the copolymer (such as properties as rubber or properties as plastic) can be adjusted.

  In addition, by appropriately selecting the central metal of the rare earth metallocene complex described below, the molar ratio of the cis 1,4-constituent unit to the total constituent units contained in the conjugated diene polymer unit (B) of the copolymer is adjusted. Can do. For example, when a copolymer is produced using 1,3-butadiene as a conjugated diene monomer, the use of a gadolinium metallocene complex may increase the molar ratio of cis 1,4-building units.

  In the production of the polymer or copolymer of the present invention, the 4-silyl-1-butene-3-yne compound to be polymerized preferably has three alkyl groups having 1 to 5 carbon atoms on the silyl element. -Trialkylsilyl-1-buten-3-yne compound. These can be polymerized alone or in combination of two or more. Needless to say, when two or more of these are polymerized in combination, a copolymer can be produced. The most preferred 4-silyl-1-butene-3-yne compound includes 4-trimethylsilyl-1-butene-3-yne.

  In the production of the copolymer of the present invention, the kind of the conjugated diene compound to be polymerized is not particularly limited, but 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2, Examples include 3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene, and two or more of these may be combined. A preferred conjugated diene compound is 1,3-butadiene.

  The polymerization catalyst is preferably a catalyst containing a metallocene complex. Further, the catalyst preferably contains an ionic compound composed of a non-coordinating anion and a cation. Further, the catalyst may optionally contain an organoaluminum compound or an aluminoxane, and may further contain other components.

  The metallocene complex is preferably a rare earth metallocene complex having a rare earth metal element as a central metal. Here, the rare earth metal element means any one of scandium Sc, yttrium Y, and lanthanoid 15 element. A metallocene complex refers to a compound in which an optionally substituted cyclopentadienyl group, indenyl group or fluorenyl group is coordinated to a central metal element.

More specifically, a polynuclear metallocene complex represented by the following general formula (α) (a binuclear metallocene complex) (having two or more central metals), or a single molecule represented by the following general formula (β): A nuclear metallocene complex (cationic metallocene complex) (one having one central metal) is preferred.

  In the general formulas (α) and (β), M may be any rare earth metal element, but is preferably gadolinium Gd, samarium Sm, neodymium Nd, or praseodymium Pr. The gadolinium complex has the highest catalytic activity for the polymerization of the complex in the present invention, and may be samarium, neodymium, and praseodymium complex in this order.

  In the general formulas (α) and (β), the type, number, and substitution position of the substituent on the cyclopentadienyl group, indenyl group, or fluorenyl group represented by Cp are not particularly limited. Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, phenyl group, benzyl group and other carbon atoms containing silicon atoms such as trimethylsilyl group A hydrogen group etc. can be mentioned. Cp may be bonded to each other via a dimethylsilylene group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, a substituted ethylene group, or the like.

In the general formulas (α) and (β), Cp is specifically a cyclopentadienyl group, methylcyclopentadienyl group, benzylcyclopentadienyl group, vinylcyclopentadienyl group, 2-methoxyethyl. Cyclopentadienyl group, trimethylsilylcyclopentadienyl group, tert-butylcyclopentadienyl group, ethylcyclopentadienyl group, phenylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3 -Dimethylcyclopentadienyl group, 1,3-di (tert-butyl) cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadiene Enyl group, pentamethylcyclopentadienyl group, 1-ethyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentadienyl 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trifluoromethyl-2, 3,4,5-tetramethylcyclopentadienyl, etc., and 1,2,3-trimethylindenyl, heptamethylindenyl, 1,2,4,5,6,7-hexa It may be a methylindenyl group or the like. Most preferred Cp is a pentamethylcyclopentadienyl group.

  In the general formula (α), X is an arbitrary bridging group or bridging atom, and bridges the rare earth metal element M and the Group III element Q of the periodic table. The bridging atom or bridging group may be a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amino group, or a hydrocarbon group having 1 to 20 carbon atoms.

Preferred halogen atoms as X in the general formula (α) are fluorine, chlorine, bromine or iodine, with chlorine and iodine being particularly preferred.
Preferred alkoxide groups or thiolate groups as X include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group or the corresponding thioalkoxy groups. Group: phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,4,6-triisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert- Aromatic alkoxy groups such as butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group, or aromatic thioalkoxy groups corresponding to these It is done. Particularly preferred are 2,6-di-tert-butylphenoxy group and 2,4,6-triisopropylthiophenoxy group.
Preferred amino groups for X include unsubstituted amino groups; lower alkyl group-substituted amino groups such as dimethylamino groups and diisopropylamino groups; phenylamino groups, 2,6-di-tert-butylphenylamino groups, 2,6- Diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neo Examples thereof include aryl-substituted amino groups such as a pentylphenylamino group and 2,4,6-tert-butylphenylamino group. Particularly preferred is a 2,4,6-tert-butylphenylamino group.
Preferred hydrocarbon groups having 1 to 20 carbon atoms as X include linear and branched alkyl groups; aromatic hydrocarbon groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group; trimethylsilyl group Etc.

  Among these, preferred as X are a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms, and most preferred is a methyl group (μ-methyl group).

  In the general formula (α), Y may be a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amino group, or a C1-20 hydrocarbon group. Preferred as Y is the same as X above, and the most preferred is a methyl group.

  In the general formula (α), Q represents a group III element in the periodic table, and boron B, aluminum Al, and gallium Ga are preferable as the element, and aluminum is particularly preferable.

In the general formula (β), Z is a non-coordinating anion, and the anion is preferably a tetravalent boron anion, such as tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl). Borate, tetrakis (trifluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl) , Pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarbaoundecaborate and the like.

  Specific examples of the polynuclear complex represented by the general formula (α) include dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadiene). Enyl) samarium, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) neodymium or dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) praseodymium.

  Specific examples of the mononuclear complex represented by the general formula (β) include bis (pentamethylcyclopentadienyl) samarium [tetrakis (pentafluorophenyl) borate], bis (pentamethylcyclopentadienyl) cerium [ Tetrakis (pentafluorophenyl) borate], bis (pentamethylcyclopentadienyl) praseodymium [tetrakis (pentafluorophenyl) borate], bis (pentamethylcyclopentadienyl) neodymium [tetrakis (pentafluorophenyl) borate], bis (Pentamethylcyclopentadienyl) gadolinium [tetrakis (pentafluorophenyl) borate] and the like.

  The complex represented by the general formula (β) can be synthesized according to the following typical reaction example using the complex represented by the general formula (α). This synthesis can also be performed with reference to the contents described in JP-A No. 2002-256012. Further, in the polymerization reaction using the polymerization catalyst containing the complex represented by the general formula (α), the complex (β) can be generated in the polymerization reaction system.

  The polymerization catalyst used for the production of the polymer or copolymer of the present invention may contain an ionic compound composed of a non-coordinating anion and a cation. In particular, when the metallocene complex contained in the polymerization catalyst is a complex represented by the general formula (α), the ionic compound is preferably contained. The ionic compound preferably reacts with a rare earth metal metallocene complex to form a cationic transition metal compound.

  As the non-coordinating anion of the ionic compound contained in the catalyst, for example, a tetravalent boron anion is preferable, and tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis ( Trifluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) ) Borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundeborate and the like.

Examples of the cation of the ionic compound contained in the catalyst include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, trialkylammonium cation such as tri (n-butyl) ammonium cation, N, N-diethylanilinium cation, N And N, N-dialkylanilinium cations such as N-2,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

That is, as the ionic compound, a combination of those selected from the non-coordinating anions and cations described above can be used. Preferably, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferro Examples include cenium tetrakis (pentafluorophenyl) borate. One ionic compound may be used, or two or more ionic compounds may be used in combination. Further, B (C ₆ F ₅ ) ₃ , Al (C ₆ F ₅ ) ₃ or the like can be used as a Lewis acid that can react with the transition metal compound to generate a cationic transition metal compound, and these can be used as the above-mentioned ions. You may use it in combination with an ionic compound.

  The polymerization catalyst used in the production of the polymer or copolymer of the present invention may contain an organoaluminum compound or a chain or cyclic aluminoxane. In particular, when the polymerization catalyst contains the complex represented by the above (β), it is preferable that the polymerization catalyst also contains an organoaluminum compound. Aluminoxane (also referred to as aluminoxane or alumoxane) is a reaction product of an organoaluminum compound and water, and is represented by the following general formula. Note that n is an arbitrary integer.

  The organoaluminum compound is preferably trialkylaluminum, and examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Particularly preferred is triisobutylaluminum.

  Examples of the aluminoxane include a reaction product of the above-described aluminum compound and water, preferably methylaluminoxane using trimethylaluminum as a raw material. Modified methylaluminoxane using a mixture of trimethylaluminum and triisobutylaluminum as a raw material can also be suitably used. As such aluminoxane, a commercially available product may be used. For example, MMAO sold by Tosoh Finechem Corporation may be used. Aluminoxane may be used alone or in combination of two or more.

  In the production of the polymer of the present invention, the rare earth metallocene complex can be used in any amount. As a standard, it is preferable to use 0.01 to 1.0 mol% with respect to the monomer 4-silyl-1-buten-3-yne compound. If the metallocene complex is made small with respect to the 4-silyl-1-buten-3-yne compound, a polymer having a large weight average molecular weight can be produced, and if it is made large, a polymer having a small weight average molecular weight is obtained. be able to.

  In the production of the copolymer of the present invention, the rare earth metallocene complex can be used in any amount. As a standard, it is preferable to use 0.01 to 1.0 mol% with respect to the total of the monomer 4-silyl-1-buten-3-yne and the conjugated diene compound.

  The amount of the ionic compound contained in the polymerization catalyst in the production of the polymer or copolymer of the present invention is preferably 0.25 to 3.0 molar equivalents relative to the metallocene complex.

  The amount of the organoaluminum compound contained in the polymerization catalyst in the production of the polymer or copolymer of the present invention is preferably 0 to 50 molar equivalents relative to the metallocene complex.

  The polymerization method used for producing the polymer or copolymer of the present invention may be any method such as a gas phase polymerization method, a solution polymerization method, a slurry polymerization method. In the case of the solution polymerization method, the solvent to be used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve 4-silyl-1-butene-3-yne, conjugated diene, and the catalyst. For example, saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; monoolefins such as 1-butene and 2-butene; aromatics such as benzene and toluene Hydrocarbons: Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene and the like. As the solvent used in the present invention, those not toxic to living organisms are preferable, and among these, aromatic hydrocarbons, particularly toluene, are preferable. One type of solvent may be used, or a mixed solvent of two or more types may be used.

  The polymerization temperature in the polymerization of the present invention is, for example, in the range of -100 to 100 ° C, preferably in the range of -50 to 80 ° C. The polymerization time is, for example, about 1 minute to 12 hours, preferably about 5 minutes to 5 hours. However, these reaction conditions can be appropriately selected according to the type and molar amount of the monomer, the type and amount of the catalyst composition, and are not limited to the ranges exemplified above. Moreover, when performing copolymerization by living polymerization, you may change conditions by superposition | polymerization of each monomer.

  After the polymerization reaction reaches a predetermined polymerization rate, a known polymerization stopper (for example, BHT (2,6-bis (t-butyl) -4-methylphenol)) is added to the polymerization system to stop it, The polymer produced according to the method can be separated from the reaction system.

The polymer or copolymer of the present invention can be identified by ¹ H-NMR analysis, ¹³ C-NMR analysis, measurement of average molecular weight and molecular weight distribution by GPC method, UV measurement, IR measurement, mass spectrometry and the like.

When the polymer or copolymer of the present invention has the structural unit represented by the general formula (I), the IR of the polymer or copolymer is measured, and the absorption characteristic of the allene bond is observed. Can be confirmed. For example, FIG. 1 shows an IR spectrum of a 4-trimethylsilyl-1-butene-3-yne polymer which is an example of the polymer of the present invention, and absorption is observed at about 1900 cm ⁻¹ . The fact that the polymer or copolymer of the present invention has the structural unit represented by the general formula (II) can be confirmed from the fact that absorption of about 2200 cm ^-1 derived from alkyne is observed in FIG.

Furthermore, the ratio of each polymer unit or each constituent unit contained in the polymer or copolymer of the present invention can be measured based on the measurement of NMR spectrum as described in the following paragraphs. Here, the NMR spectrum was measured under the conditions of a frequency of 300 MHz ( ¹ H) 7.5 MHz ( ¹³ C), a measurement temperature: 25 ° C., and a measurement solvent: deuterated chloroform. It can be performed using an NMR measuring apparatus.

The ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) contained in the polymer or copolymer of the present invention is ¹³ C- It can be calculated from the integration ratio of NMR peaks. For example, FIG. 2 is a ¹³ C-NMR measurement chart of a 4-trimethylsilyl-1-butene-3-yne polymer which is an example of the polymer of the present invention. Here, the peak at δ205-207 ppm is attributed to the central carbon of the allene bond in the following general formula (I ′), and the peak at 108-112 ppm is on the acetylene carbon to which the trimethylsilyl group in the following general formula (II ′) is bonded. Since it is attributed, it can be determined by comparing the integrated values of both peaks.

The ratio of the conjugated diene polymer unit and the 4-silyl-1-butene-3-yne polymer unit in the copolymer of the present invention is calculated from the integral ratio of the characteristic ¹ H-NMR peaks of both polymer units. can do. For example, FIG. 3 is a ¹ H-NMR measurement chart of a copolymer containing 4-trimethylsilyl-1-butene-3-yne polymerized units and 1,3-butadiene polymerized units, which is an example of the copolymer of the present invention. is there. Here, the peak at 0.1-0.2 ppm is attributed to the hydrogen atom of the trimethylsilyl group of the 4-trimethylsilyl-1-butene-3-yne polymer unit, and the peak at 4.8-5.0 ppm is represented by the following general formula (VII The peak at 5.3-5.5 ppm, which is assigned to one hydrogen atom of geminal hydrogen of the 1,2-constituent unit represented by '), is a 1,2-constituent unit represented by the general formula (VII') And the other one hydrogen atom of the cis and trans 1,4-constituent units represented by the following general formulas (V ′) and (VI ′). Therefore, the ratio between the conjugated diene polymerized unit and the 4-silyl-1-butene-3-yne polymerized unit can be determined by determining the integrated value of these peaks.

Cis 1,4-constituent unit (V) contained in conjugated diene polymer unit contained in copolymer of the present invention
And trans 1,4-structural unit (VI), and 1,2-structural unit (VII), respectively. The ratio of the ¹ H-NMR and ¹³ C-NMR peaks characteristic of each constituent unit It can be calculated from For example, as described above, the peak at 4.8-5.0 ppm in FIG. 3 is attributed to one of geminal hydrogens of 1,2-structural unit (VII ′), and the peak at 5.3-5.5 ppm is 1 , 2- The structural unit (VII ') is assigned to the remaining one of the geminal hydrogens, and the cis and trans 1,4-building units (V') and (VI '), respectively, to two vinyl hydrogens, The ratios of the cis 1,4-constituent unit (V), the trans 1,4-constituent unit (VI), and the 1,2-constituent unit (VII) can be determined from the integrated values of the peaks. FIG. 4 is a measurement chart of ¹³ C-NMR of the copolymer. The peak at 27.4 ppm in FIG.
The peak at 32.7 ppm is attributed to the saturated carbon of the structural unit (V ″) and the peak at 127.7-131.8 ppm is attributed to the saturated carbon of the trans 1,4-structural unit (VI ″). And trans 1,4- attributed to the vinyl carbon of the structural units (V ″) and (VI ″). Moreover, the peaks of 113.8-114.8 and 143.3-144.7 are attributed to the vinyl carbon of the 1,2-structural unit (VII ″) (the peaks are so small that they cannot be detected in FIG. 4). ). Therefore, by calculating the integrated values of these peaks, the ratios of cis 1,4-building unit (V), transformer 1,4-building unit (VI), and 1,2-building unit (VII) are obtained. It is possible.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples.
Cp * means “pentamethylcyclopentadienyl”.
<Production Example of 4-Trimethylsilyl-1-butene-3-yne Polymer>
[Example 1]

In a glove box under a nitrogen atmosphere, in a well-dried 30 ml pressure-resistant glass bottle, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ] was charged in 0.01 mmol and dissolved in 4 ml of toluene. Next, 0.15 mmol of triisobutylaluminum and 0.01 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) were added and the bottle was stoppered. Thereafter, the bottle was taken out from the glove box, charged with 1.0 ml of 4-trimethylsilyl-1-butene-3-yne (trimethylsilylvinylacetylene: TMSVA), and polymerized at room temperature for 1 hour.
After the polymerization, 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and a large amount of methanol / hydrochloric acid mixed solvent was added to obtain a polymer. Separate and vacuum dry at 60 ° C.
Yield of the obtained polymer: 100 wt%
Polymer microstructure: 1,4-adduct 21.7mol%, vinyl (1,2-) adduct 78.3mol%
Weight average molecular weight: 141,500
Molecular weight distribution Mw / Mn: 2.11
[Example 2]

In Example 1, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( The experiment was conducted in the same manner except that pentamethylcyclopentadienyl) samarium [(Cp *) ₂ Sm (μ-Me) ₂ AlMe ₂ ] was used.
Yield of the obtained polymer: 72 wt%
Polymer microstructure: 1,4-adduct 19.1mol%, vinyl (1,2-) adduct 80.9mol%
Weight average molecular weight: 158,600
Molecular weight distribution Mw / Mn: 1.71
[Example 3]

In Example 1, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( Experiments were conducted in the same manner except that pentamethylcyclopentadienyl) neodymium [(Cp *) ₂ Nd (μ-Me) ₂ AlMe ₂ ] was used.
Yield of the obtained polymer: 53 wt%
Polymer microstructure: 1,4-adduct 17.2mol%, vinyl (1,2-) adduct 82.8mol%
Weight average molecular weight: 134,000
Molecular weight distribution Mw / Mn: 1.23
[Example 4]

In Example 1, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( The experiment was conducted in the same manner except that pentamethylcyclopentadienyl) praseodymium [(Cp *) ₂ Pr (μ-Me) ₂ AlMe ₂ ] was used and the polymerization time was changed from 1 hour to 2 hours.
Yield of the obtained polymer: 12 wt%
Polymer microstructure: 1,4 adduct 19.2mol%, vinyl (1,2-) adduct 80.8mol%
Weight average molecular weight: 128,100
Molecular weight distribution Mw / Mn: 1.27

<Example of production of a copolymer of 4-trimethylsilyl-1-butene-3-yne and 1,3-butadiene>
[Example 5]

A well-dried 30 ml pressure-resistant glass bottle was charged with 1.0 ml of toluene, 0.27 g of 1,3-butadiene and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne, and the bottle was stoppered. A catalyst solution (dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ] 0.01 mmol, triisobutyl prepared in advance 0.15 mmol of aluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate Ph ₃ CB (C ₆ F ₅ ) ₄ 0.01 mmol dissolved in 2 ml of toluene) were added, and polymerization was performed at room temperature for 1 hour.
After the polymerization, 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and a large amount of methanol / hydrochloric acid mixed solvent was added to obtain a polymer. Separate and vacuum dry at 60 ° C.
Yield of the obtained polymer: 0.54 g
Content of butadiene polymer units in the copolymer: 28.7 mol%
1,4-cis content in the microstructure of butadiene polymer units: 75 mol%
Content of 1,4-constituent unit in 4-trimethylsilyl-1-butene-3-yne polymer unit: 33.1 mol%
Weight average molecular weight: 203,400
Molecular weight distribution Mw / Mn: 3.06
[Example 6]

In Example 5, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( The experiment was conducted in the same manner except that pentamethylcyclopentadienyl) samarium [(Cp *) ₂ Sm (μ-Me) ₂ AlMe ₂ ] was used.
Yield of the obtained polymer: 0.32 g
Content of butadiene polymer units in the copolymer: 26.7 mol%
1,4-cis content in the microstructure of butadiene polymer units: 62 mol%
Content of 1,4-constituent unit in 4-trimethylsilyl-1-butene-3-yne polymerized unit: 33.2%
Weight average molecular weight: 209,700
Molecular weight distribution Mw / Mn: 2.66
[Example 7]

In Example 5, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( The experiment was conducted in the same manner except that pentamethylcyclopentadienyl) neodymium [(Cp *) ₂ Nd (μ-Me) ₂ AlMe ₂ ] was used.
Yield of the obtained polymer: 0.29 g
Content of butadiene polymer unit in the polymer: 25.1 mol%
1,4-cis content in the microstructure of butadiene polymer units: 58 mol%
Content of 1,4-constituent unit in 4-trimethylsilyl-1-butene-3-yne polymer unit: 34.2%
Weight average molecular weight: 195,400
Molecular weight distribution Mw / Mn: 1.99
[Example 8]

In Example 5, instead of dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ], dimethylaluminum (μ-dimethyl) bis ( The experiment was conducted in the same manner except that pentamethylcyclopentadienyl) praseodymium [(Cp *) ₂ Pr (μ-Me) ₂ AlMe ₂ ] was used and the reaction time was changed from 1 hour to 2 hours.
Yield of the obtained polymer: 0.24 g
Content of butadiene units in polymer: 24.5 mol%
1,4-cis content in the microstructure of butadiene polymer units: 45 mol%
Content of 1,4-constituent unit in 4-trimethylsilyl-1-butene-3-yne polymer unit: 32.9%
Weight average molecular weight: 185,700
Molecular weight distribution Mw / Mn: 1.78
[Example 9]

In Example 5, an experiment was conducted in the same manner except that 0,27 g of 1,3-butadiene was changed to 0.39 g and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 0.48 ml. Yield of the obtained polymer: 0.52 g
Content of butadiene polymer unit in polymer: 66.1 mol%
1,4-cis content in the microstructure of butadiene polymer units: 78 mol%
Weight average molecular weight: 147,900
Molecular weight distribution Mw / Mn: 2.98
[Example 10]

In Example 5, the experiment was conducted in the same manner except that 0,27 g of 1,3-butadiene was changed to 0.49 g and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 0.16 ml.
Yield of the obtained polymer: 0.54 g
Content of butadiene polymer unit in polymer: 94.8 mol%
1,4-cis content in the microstructure of butadiene polymer units: 98 mol%
Weight average molecular weight: 273,800
Molecular weight distribution Mw / Mn: 2.52
[Example 11]

In Example 5, an experiment was conducted in the same manner except that 0,27 g of 1,3-butadiene was changed to 0.97 g and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 0.16 ml. Yield of the obtained polymer: 0.82 g
Content of butadiene units in the polymer: 96.0 mol%
Weight average molecular weight: 572,400
Molecular weight distribution Mw / Mn: 3.37
[Example 12]

In Example 5, the experiment was conducted in the same manner except that 0,27 g of 1,3-butadiene was changed to 1.94 g and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 0.16 ml.
Yield of the obtained polymer: 1.31 g
Content of butadiene polymer unit in polymer: 97.6 mol%
Weight average molecular weight: 934,600
Molecular weight distribution Mw / Mn: 2.79
[Example 13]

In Example 5, the experiment was conducted in the same manner except that 0,27 g of 1,3-butadiene was changed to 0.11 g and 0.8 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 1.28 ml. Yield of the obtained polymer: 0.97 g
Content of butadiene polymer unit in polymer: 9.3 mol%
1,4-cis content in the microstructure of butadiene units: 51 mol%
Weight average molecular weight: 140,400
Molecular weight distribution Mw / Mn: 1.79
[Example 14]

A well-dried 100 ml pressure-resistant glass bottle was charged with 56.0 ml of toluene, 13.5 g of 1,3-butadiene, and 1.5 ml of 4-trimethylsilyl-1-butene-3-yne, and the bottle was stoppered. A catalyst solution (dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(Cp *) ₂ Gd (μ-Me) ₂ AlMe ₂ ] 0.05 mmol, triisobutyl prepared beforehand Aluminum (0.75 mmol) and triphenylcarbenium tetrakis (pentafluorophenyl) borate Ph ₃ CB (C ₆ F ₅ ) ₄ 0.05 mmol dissolved in 4 ml of toluene) were added, and polymerization was performed at room temperature for 3 hours.
After the polymerization, 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and a large amount of methanol / hydrochloric acid mixed solvent was added to obtain a polymer. Separate and vacuum dry at 60 ° C.
Yield of the obtained polymer: 3.96 g
Content of butadiene polymer unit in polymer: 93.6 mol%
Weight average molecular weight: 1,688,400
Molecular weight distribution Mw / Mn: 3.23
[Example 15]

In Example 14, an experiment was performed in the same manner except that 1.5 ml of 4-trimethylsilyl-1-buten-3-yne was changed to 3.5 ml.
Yield of the obtained polymer: 5.17 g
Content of butadiene polymer unit in polymer: 83.0 mol%
Weight average molecular weight: 886,500
Molecular weight distribution Mw / Mn: 2.67
[Example 16]

In Example 14, an experiment was performed in the same manner except that 1.5 ml of 4-trimethylsilyl-1-butene-3-yne was changed to 5.5 ml.
Yield of the obtained polymer: 7.94 g
Content of butadiene polymer unit in polymer: 78.5 mol%
Weight average molecular weight: 692,200
Molecular weight distribution Mw / Mn: 3.14

It is a measurement chart of IR of 4-trimethylsilyl-1-butene-3-yne polymer. Absorption derived from allene bonds and absorption derived from alkynes are observed. It is a ¹³ C-NMR measurement chart of 4-trimethylsilyl-1-butene-3-yne polymer. It is a ¹ H-NMR measurement chart of a copolymer containing 4-trimethylsilyl-1-butene-3-yne polymerized units and 1,3-butadiene polymerized units. It is a ¹³ C-NMR measurement chart of a copolymer containing 4-trimethylsilyl-1-butene-3-yne polymerized units and 1,3-butadiene polymerized units.

Claims (13)

4-silyl-1-butene-3-yne polymer containing the structural unit represented by the following general formula (I), and the structural unit represented by general formula (II).

  The molar ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) contained in the polymer is (I) :( II) = 10: 90 to 100: 0. The polymer according to claim 1, wherein the polymer falls within the range of The polymer according to claim 1 or 2, wherein R ¹ in the general formulas (I) and (II) are all methyl groups.   A copolymer comprising 4-silyl-1-butene-3-yne polymerized units (A) and conjugated diene polymerized units (B). The 4-silyl-1-butene-3-yne polymer unit (A) includes a structural unit represented by the following general formula (I) and a structural unit represented by the general formula (II). The copolymer according to claim 4.

  The molar ratio of 4-silyl-1-butene-3-yne polymer unit (A) to conjugated diene polymer unit (B) in the copolymer is (A) :( B) = 95: 5 to 2:98. 6. Copolymer according to claim 4 or 5, characterized in that it falls within the range.   The molar ratio of cis 1,4-structural units to all structural units contained in the conjugated diene polymerized unit (B) is in the range of 20 to 100 mol%, according to any one of claims 4 to 6. The copolymer according to one item.   The copolymer according to any one of claims 4 to 7, wherein the conjugated diene is 1,3-butadiene.   The copolymer according to any one of claims 4 to 8, wherein the 4-silyl-1-butene-3-yne is 4-trimethylsilyl-1-butene-3-yne.   The method for producing a polymer according to any one of claims 1 to 3, comprising a step of polymerizing a 4-silyl-1-buten-3-yne compound using a catalyst containing a rare earth metal metallocene complex.   The copolymer according to any one of claims 4 to 9, comprising a step of polymerizing a 4-silyl-1-buten-3-yne compound and a conjugated diene compound using a catalyst containing a rare earth metal metallocene complex. How to manufacture. The method according to claim 10 or 11, wherein the rare earth metal metallocene complex is a complex represented by the following general formula (α).

  The method according to any one of claims 10 to 12, wherein the catalyst further comprises an ionic compound comprising a non-coordinating anion and a cation.

Images